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Post-synthetic Modification of Zirconium Metal-Organic Frameworks by Catalyst-Free aza-Michael Additions

Post-synthetic Modification of Zirconium Metal-Organic Frameworks by Catalyst-Free aza-Michael Additions

Harina Amer Hamzah, Tom S Crickmore, Daniel Rixson, Andrew D Burrows

Dalton Trans. 2018 Oct 23;47(41):14491-14496.

PMID: 30256351

Abstract:

The reactions of the zirconium MOF [Zr6O4(OH)4(bdc-NH2)6] (UiO-66-NH2, bdc-NH2 = 2-amino-1,4-benzenedicarboxylate) with the Michael acceptors acrylonitrile (CH2[double bond, length as m-dash]CHCN), acrylic acid (CH2[double bond, length as m-dash]CHCO2H), methyl acrylate (CH2[double bond, length as m-dash]CHCO2Me) and methyl vinyl ketone (CH2[double bond, length as m-dash]CHC(O)Me) led to post-synthetic modification of the MOF through C-N bond formation without loss of crystallinity. The reactions with acrylonitrile and acrylic acid go to completion, yielding [Zr6O4(OH)4(bdc-NHCH2CH2CN)6] (UiO-66-AN, 1) and [Zr6O4(OH)4(bdc-NHCH2CH2CO2H)6] (UiO-66-AA, 2) respectively, whereas those with methyl acrylate and methyl vinyl ketone are incomplete, yielding [Zr6O4(OH)4(bdc-NH2)0.66(bdc-NHCH2CH2CO2Me)5.34] (UiO-66-MA, 3) and [Zr6O4(OH)4(bdc-NH2)2.76(bdc-NHCH2CH2C(O)Me)3.24] (UiO-66-MVK, 4), respectively. The acrylonitrile-modified MOF UiO-66-AN undergoes further reaction with sodium azide in the presence of zinc(ii) chloride in n-butanol to form the tetrazolate-modified MOF [Zr6O4(OH)4(bdc-NHCH2CH2CN)4.74(bdc-NHCH2CH2CN4H)1.26] (UiO-66-TZ, 5).

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP60653578	Zirconium acrylate		60653-57-8	Price

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